Azide interaction with 4f and 5f ions in aqueous solutions. 1. Trivalent ions

Musikas, C.; Cuillerdier, C.; Livet, J.; Forchioni, A.; Chachaty, C.

doi:10.1021/ic00160a010

Cited by 23 publications

(16 citation statements)

References 3 publications

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“…A number of soft (S‐ and N‐) donor ligands have been evaluated extensively during the last few decades . Musikas et al have reported the selective complexation of trivalent actinides over lanthanides with azide ions, which is the first example of actinide selectivity employing N‐donor ligands . A number of terdentate N‐donor heteropolycyclic ligands, namely terpyridine, 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (TPTZ), bis(1,2,4‐triazinyl)pyridine (R‐BTP), have been evaluated subsequently for the mutual separation of trivalent actinides and lanthanides.…”

Section: Introductionmentioning

confidence: 99%

An Insight into the Complexation of Trivalent Americium Vis‐à‐Vis Lanthanides with Bis(1,2,4‐triazinyl)bipyridine Derivatives

Bhattacharyya¹,

Mohapatra²,

Mohapatra³

et al. 2016

Eur J Inorg Chem

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Complexation of Am 3+ and Ln 3+ (La 3+ , Eu 3+ , and Er 3+ ) with two bis(1,2,4-triazinyl)bipyridine (C 2 BTBP, C 5 BTBP) derivatives has been studied in acetonitrile medium with use of various experimental techniques such as electrospray ionization mass spectrometry (ESI-MS), time-resolved fluorescence spectroscopy (TRFS), UV/Vis spectrophotometry, and solution calorimetry. Metal-ligand stoichiometries and conditional stability constants of these complexes were determined. To the best of our knowledge, this is the first report on the complexation of

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Section: Introductionmentioning

confidence: 99%

An Insight into the Complexation of Trivalent Americium Vis‐à‐Vis Lanthanides with Bis(1,2,4‐triazinyl)bipyridine Derivatives

Bhattacharyya¹,

Mohapatra²,

Mohapatra³

et al. 2016

Eur J Inorg Chem

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“…Another reason for that choice is that gases based on N donor atoms have been suggested for industrial partitioning of f-block elements, namely for selective extraction of the Am and Cm minor actinoids from lanthanoid fission products. 29,30 Such fundamental understanding of the chemical reactivity between Ln + and NH 3 gas requires associated theoretical calculations, in order to dissect more precisely the mechanisms of the chemical reactions including stable conformers formed, transition states and energetics of the reactions. Very few theoretical studies have been published on mono-cations of f-block elements in the literature.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

Quemet

Vitorge

Cimas

et al. 2013

International Journal of Mass Spectrometry

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The reactivity of La + , Sm + , Eu + and Gd + with NH 3 (g) and ND 3 (g) is studied in the reaction cell of a quadrupole ICP-MS. For Ln + = La + and Gd + , the primary reaction channel is the formation of the LnNH + protonated nitride leading to H 2 elimination. The LnNH(NH 3) + 1-5 ammonia complexes of the Ln protonated nitride are further generated. Sm + and Eu + are much less reactive: the protonated nitride is not detected, and only small amounts of Ln(NH 3) 0-6 + are observed. DFT, MP2, CCSD(T) and CASSCF/CASPT2 calculations are used to explore the potential energy surfaces. For the La + and Gd + ions of f-block elements, the reaction pathways have three steps: first the formation of LnNH 3 + , then the isomerization to HLnNH 2 + , and finally the loss of H 2 associated with the formation of a Ln-N triple bond in the final product LnNH +. On the other hand, Sm + and Eu + are not able to form stable complexes. This was rationalized in terms of energy barriers for the chemical reactions and electronic promotion energies for these Ln + atoms.

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“…Less strictly but more descriptively, we can say that because of lower relative abundance of the MX 3 innersphere species, the distribution ratios from azide and cyanate solutions are lower than from thiocyanate and selenocyanate solutions. According to paper [7] the lanthanide thiocyanate complexes with the 1:1 ligand to metal ratio are outer-sphere, while the respective azide complexes are inner-sphere [10,17]. If so, then from our results the /?…”

Section: Effect Of the Ligand On Stability Constantsmentioning

confidence: 57%

The Effect of the Pseudohalide Ligand on Solvent Extraction of Trivalent Lanthanides, Yttrium and Americium by Tri-n-Butyl Phosphate

Borkowski

Krejzler²,

Siekierski

1994

Radiochimca Acta

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Solvent extraction of Y, Am(III) and some lanthanides from thiocyanate, selenocyanate, cyanate and azide solutions by tri-nbutyl phosphate was studied. It has been found that the distribution ratio, D, is high for thiocyanates and selenocyanates and very low for azides and cyanates. At the same time the separation factor D An /£> Y is about 12 for the NCS" and NCSe" ligands, while for the NCO" and N 3 " ligands the separation factors between Am and Y, and between all the elements studied are very close to one. The division of the isoelectronic pseudohalide ligands into two classes with respect to D and to separation factors corresponds with the division of the respective hydracids into moderately strong (HNCS and HNCSe) and weak (HNCO and HN 3 ). The results are discussed in terms of the effect of the pseudohalide anion, X", on the stability and transfer of the innersphere MX 3 complexes, and on the equilibrium between the inner-and outer-sphere complexes in the aqueous phase.

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Azide interaction with 4f and 5f ions in aqueous solutions. 1. Trivalent ions

Cited by 23 publications

References 3 publications

An Insight into the Complexation of Trivalent Americium Vis‐à‐Vis Lanthanides with Bis(1,2,4‐triazinyl)bipyridine Derivatives

An Insight into the Complexation of Trivalent Americium Vis‐à‐Vis Lanthanides with Bis(1,2,4‐triazinyl)bipyridine Derivatives

Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

The Effect of the Pseudohalide Ligand on Solvent Extraction of Trivalent Lanthanides, Yttrium and Americium by Tri-n-Butyl Phosphate

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